US5980648A - Cleaning of workpieces having organic residues - Google Patents
Cleaning of workpieces having organic residues Download PDFInfo
- Publication number
- US5980648A US5980648A US08/107,696 US10769693A US5980648A US 5980648 A US5980648 A US 5980648A US 10769693 A US10769693 A US 10769693A US 5980648 A US5980648 A US 5980648A
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- US
- United States
- Prior art keywords
- pressure tank
- liquefied
- supercritical gas
- process according
- cleaning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/102—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration with means for agitating the liquid
- B08B3/104—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration with means for agitating the liquid using propellers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0021—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by liquid gases or supercritical fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0064—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by temperature changes
- B08B7/0092—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by temperature changes by cooling
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
Definitions
- the invention relates to a process for cleaning workpieces exhibiting organic residues, with the use of a fluid introduced under pressure into a pressure tank loaded with the workpieces.
- a gas compressed to its supercritical pressure or thereabove is conducted onto the workpieces to be cleaned in a pressure tank.
- the temperature of the thus-compressed gas is varied, starting with a point in the proximity of the critical temperature, in various steps, in order to influence the dissolving properties of the gaseous phase.
- the temperature is kept constant for a specific time interval.
- Cleaning of the workpieces can furthermore be additionally enhanced by introducing into the compressed gas a liquid, such as deionized water, a chemically reactive compound, or sound or radiation energy.
- a further drawback of this process occurs during emptying of the pressure tank.
- the gas mass compressed to supercritical pressure contains the residual compounds in solution after the cleaning step.
- the pressure and temperature of the mass of gas must be kept constant while it is removed.
- pure gas compressed to supercritical pressure is replenished while the contaminated gas is discharged from the pressure tank. Only after the entire content of the tank consisting of contaminated gas has thus been removed is it possible to lower the pressure and to take out the workpieces. In this process, it is highly probable that the contaminated gas mass has merely been diluted, rather than replaced, and that during lowering of the pressure the remaining, dissolved residual compounds will again be precipitated. Additionally, exchanging of the entire content of the tank after each cleaning step is not economical.
- the invention is based on the object of developing a process for cleaning workpieces contaminated with organic residues with the use of a fluid, avoiding the aforementioned disadvantages and increasing the success of the cleaning procedure in an economical fashion.
- This object has been attained according to the invention by circulating the fluid in the pressure tank during the cleaning step.
- the process of this invention represents a simple measure considerably enhancing the cleaning operation.
- the fluid understood to mean a gaseous, liquid or also supercritical substance, is mechanically circulated in the pressure tank, for example, by the rotation of a vane-equipped impeller.
- the thus-initiated flow of fluid in the pressure tank brings about a continuous exchange of pure fluid and of fluid loaded with dissolved impurities. Thereby, the organic residues adhering to the workpiece surfaces can be successively removed in their entirety.
- the circulating velocity is advantageously varied during the cleaning step.
- This change can take place, for example, by cyclically varying the number of revolutions of an impeller producing the circulation.
- the result is achieved that the suction zones and pressurized zones of the fluid, produced during the circulation, are altered in their cross section, and that simultaneously an effect can be exerted on the velocity distribution of the fluid.
- This feature prevents the formation of regions in the pressure tank wherein, at a constant speed of the impeller, no fluid circulation would occur.
- a liquefied gas as the fluid is advantageous; this gas is conducted into the pressure tank at a suitable pressure, dissolves the residual compounds off the workpiece surfaces in the tank, and forms a unitary phase with these compounds.
- Determining factors for the solubility of the substance in the fluid are, besides the vapor pressure of the substance to be dissolved and the density and temperature of the fluid, also polarity and molecular weight of the substance, as well as viscosity, diffusion coefficient, critical point, and dipole moment of the fluid, along with the molecular interactions of this fluid with the substance. Simple, generally valid rules cannot be established for different substances and fluids.
- Suitable fluids for removing organic residues are, for example, noble gases, such as helium or argon, hydrocarbons, i.e., for example, alkanes, such as methane, ethane or propane, or alkenes, such as ethene or propene, as well as trifluoromethane, carbon dioxide, nitrous oxide, and sulfur hexafluoride.
- noble gases such as helium or argon
- hydrocarbons i.e., for example, alkanes, such as methane, ethane or propane
- alkenes such as ethene or propene
- trifluoromethane carbon dioxide, nitrous oxide, and sulfur hexafluoride
- Carbon dioxide is not flammable or explosive; carbon dioxide is cheaply available in large amounts as a by-product of industrial processes; carbon dioxide, in contrast to other solvents, exerts a low stress on the environment; and carbon dioxide has a chemically inert behavior. Besides, the thermodynamic properties of carbon dioxide are favorable for the process according to this invention.
- a suitable measure in conducting the process of the invention resides in keeping the temperature of the fluid in the pressure tank constant during the cleaning step.
- the suitable parameters, temperature and pressure of the fluid, for removing the organic residues are first determined in preliminary tests. These parameters are then maintained constant during the cleaning procedure.
- a portion of the fluid is continuously withdrawn from the pressure tank, passed through a heat exchanger, and subsequently reintroduced into the pressure tank. Heating of the fluid may be necessary during long-term cleaning processes in pressure tanks that are not thermally insulated; on the other hand, cooling of the fluid may be needed, above all in heat-insulated containers if the energy supplied for the circulation of the fluid heats up the latter.
- the heat exchange of the fluid is also suitable for covering a specific temperature range during the cleaning step if this should be necessary.
- An improper pressure rise can be prevented depending on the physical condition of the fluid by means of a pressure relief valve or by means of an overflow regulator at the pressure tank.
- the fluid contaminated with the organic residues must be removed from the pressure tank; the cleaned workpieces are discharged subsequently.
- the fluid containing the residues thus discharged from the pressure tank, is then expanded whereby the organic residues are separated from the fluid.
- the expansion brings about a separation of the binary phase consisting of the fluid and the organic residues because the organic residues pass over almost entirely into a liquid phase whereas the fluid is present in most cases in the gaseous phase.
- the expansion additionally results in a solid phase in the form of carbon dioxide snow.
- the potential energy of the fluid liberated during expansion is utilized for driving a turbine.
- a suitable apparatus for performing the process according to the invention is characterized in that a first cylindrical pressure tank contains an impeller attached to its axle within the pressure tank; that the first pressure tank is connected with an analogously equipped second pressure tank by way of conduits provided with valves; that a pump is arranged in one of the connecting conduits, and a heat exchanger is arranged in this pump or in another connecting conduit, wherein the heat exchanger and the pump are each connected with each pressure tank by additional conduits; and that each pressure tank is connected with one or several storage tanks for fluids by means of additional conduits.
- Each pressure tank 38, 39 contains an impeller 6 effecting the circulation of the fluid and separated by a protective screen 5 from the remaining interior of the pressure tank 38, 39.
- the impeller 6 is driven externally of the pressure tank 38, 39 via the shaft 9 and is supported in a stuffing bush 8.
- a fixedly mounted guide rail 12 is located for a tubular slide carrying the workpieces to be cleaned.
- the pressure tank 38, 39 is tightly sealed by a high-pressure lid 7.
- Each pressure tank 38, 39 furthermore contains a manometer 3, 34 and safety valve units 4, 35, as well as respectively one level sensor 10, 31 and a pressure switch 11, 32.
- the pressure tanks 38, 39 are in communication with each other via several conduits.
- a direct connecting conduit contains two shutoff ball cocks 2, 33 and a motor-driven control valve 29.
- a heat exchanger 20 is connected by means of conduits via the motor-driven control valves 13, 15, 14 with the pressure tank 38 and via the control valves 27, 15, 28 with the pressure tank 39.
- This heat exchanger 20 contains a temperature regulator 21 and a safety valve 22.
- a pump 19 is connected by means of conduits via the motor-driven control valves 13, 17, 14 with the pressure tank 38 and via the control valves 27, 17, 28 with the pressure tank 39.
- a safety valve 23 is likewise arranged in the pump conduit.
- both pressure tanks 38, 39 are connected with each other by conduits by way of the heat exchanger 20 and the control valves 13, 15, 28, as well as by way of the pump 19 and the control valves 13, 17, 28.
- a storage tank for a fluid is utilized wherein the latter is present under pressure in compressed and partially liquefied form.
- the fluid can be withdrawn from the top section of this storage tank in the gaseous phase, from the bottom section of this storage tank in the liquid phase, and can be introduced into the two pressure tanks 38, 39.
- the gaseous fluid can be conducted via the heat exchanger 20 by way of the control valves 16, 15, 14 into the pressure tank 38 and by way of the control valves 16, 15, 28 into the pressure tank 39.
- the liquid fluid is fed via the pump 19 by way of the control valves 18, 17, 14 to the pressure tank 38 and by way of the control valves 18, 17, 28 to the pressure tank 39.
- fluid can be returned from the pressure tank 38 into the storage tank.
- gaseous fluid can be returned via the overflow regulator 1 and the control valve 36, and liquid fluid via the overflow regulator 1 and the control valve 37 into the storage tank.
- fluid can be returned into the storage tank from the pressure tank 39 in a completely analogous fashion.
- the apparatus of this invention comprises a venting facility wherein the dissolved organic residues are separated from the fluid by expansion.
- the fluid can furthermore be conducted into a turbine which renders part of the energy liberated during expansion reusable in that it converts this energy into rotational energy and utilizes the latter for current generation.
- This venting facility is connected to the conduit system between the two pressure tanks 38, 39 by way of a probe for liquid fluid 26 and a motor-driven control valve 25. Consequently, fluid exhausted after the cleaning step can be conducted from the pressure tanks 38, 39 into the venting facility.
- the process according to this invention serves, in the embodiment, for cleaning just-manufactured copper tubes, the surfaces of which are coated with drawing grease from the manufacturing procedure.
- Approximately 700 to 800 copper tubes are loaded onto respectively one tubular slide, and these slides are then moved on the guide rails 12 into the two pressure tanks 38, 39. Then the high-pressure lids 7 are sealed.
- carbon dioxide is utilized as the fluid, withdrawn from a storage tank under pressure at a room temperature of about 298 Kelvin.
- the carbon dioxide flows in the gaseous phase through the conduits into the pressure tank 38 with the control valves 16, 15 and 14 being opened, until pressure equalization has been obtained with the storage tank.
- the temperature of the gas is kept constant at about 298 Kelvin by the heat exchanger 20.
- the pressure of the carbon dioxide gas at this temperature then is about 64 bar in the pressure tank 38. Cooling of the gas should be prevented inasmuch as this would lead to congealing of the oily residues adhering to the tubes and would thereby make the cleaning process more difficult.
- the pressure tank 38 is thus initially pressurized. Now liquid carbon dioxide can be passed into the pressure tank 38 without there being an expansion of the liquefied gas.
- the communication to the top section of the storage tank is sealed off, the control valves 18, 17 and 14 are opened, and liquid carbon dioxide is conducted from the bottom section of the storage tank via the pump 19 into the pressure tank 38.
- the carbon dioxide gas during this step, is forced back into the storage tank by the inflowing liquid from the pressure tank 38 via the overflow regulator 1, with the control valve 36 being open.
- the level sensor 10 shuts off the pump 19 once the desired filling level has been attained.
- the pressure tank 38 is now filled with liquid carbon dioxide.
- good cleaning results were achieved at temperatures of between 298 Kelvin and 304 Kelvin, the pressure being somewhat above the corresponding vapor pressure values.
- Corresponding conditions are now established in the pressure tank 38; the temperature of the liquid carbon dioxide can be regulated with the aid of heat exchanger 20.
- the cleaning process is performed by circulating the liquid carbon dioxide in the pressure tank 38.
- the impeller 6 is driven by way of the shaft 9, the number of revolutions of the impeller 6 being cyclically varied by means of a time control. Thereby, the zone wherein no circulation takes place at constant speed is shifted over the diameter of the pressure tank 38.
- the circulating action causes a stream of carbon dioxide conducting continuously new amounts of carbon dioxide to the tube surfaces whereby the dissolving capacity of the entire volume of carbon dioxide in the pressure tank 38 can be exploited, and the cleaning step proceeds substantially faster and more efficient than in case of stationary contact.
- the oily residues on the copper tubing are detached and pass over into a unitary phase with the liquid carbon dioxide.
- the cleaning step takes approximately one-half hour. In general, this time period is varied in dependence on the extent of contamination of the copper tubes.
- pressurizing of the pressure tank 39 is begun.
- gaseous carbon dioxide is conducted from the storage tank via the heat exchanger 20 into the pressure tank 39 with the valves 16, 15 and 28 being open.
- liquid carbon dioxide is pumped from the storage tank via the pump 19 into the pressure tank 39 with the valves 18, 17 and 28 being opened.
- this time only a part of the tank volume is filled with liquid carbon dioxide. This part is dimensioned in accordance with the number of cleaning steps required for saturating the entire amount of liquid carbon dioxide in the tank with the oil residues. In this embodiment, this number is about 7 to 8 cleaning steps, i.e.
- valves 13, 17 and 28 are opened, and liquid carbon dioxide, now already containing the oily residues in solution, is pumped from the pressure tank 38 into the pressure tank 39.
- the gas utilized for pressurizing the pressure tank 39 is conducted into the pressure tank 38 during this procedure.
- the shutoff ball cocks 33 and 2 as well as the control valve 29 are opened up.
- the level sensor 31 terminates the filling step with liquid carbon dioxide.
- the cleaning step then takes place in the pressure tank 39 in a completely analogous way as already described for the pressure tank 38.
- the pressure tank 38 contains the cleaned copper tubes, the remaining quantity of liquid carbon dioxide containing the oily residues, as well as the pure carbon dioxide gas introduced for maintaining the pressure.
- This carbon dioxide gas introduced into pressure tank 39 from pressure tank 38, causes an excess pressure ranging above the excess pressure prevailing during the cleaning step, on account of the remaining amount of liquid in the pressure tank 38, whereby it is ensured during the subsequent removal of the liquid carbon dioxide containing the oil residues that the latter remain dissolved in the liquid carbon dioxide. This is so because thereby no expansion of the liquid carbon dioxide can take place to pressures ranging lower than during the cleaning step.
- the pressure In order to remove the workpieces from the pressure tank 38, the pressure must be lowered to atmospheric pressure.
- the circulation of the gas is initiated when the probe 26 registers only gaseous carbon dioxide any more.
- the valves 13, 15 and 14 are then opened, and a portion of the gas is conducted through the heat exchanger 20 on account of the flow pressure produced during circulation.
- the valve 25 remains open so that a component stream of the gas is exhausted from the pressure tank 38.
- pressure lowering occurs at a temperature that is maintained constant. A sudden expansion of the carbon dioxide gas to normal pressure is accordingly prevented; such an event would cause the formation of carbon dioxide snow and therefore also a strong cooling of the system.
- the effluent carbon dioxide gas, freed of the oily residues, can, of course, be passed again to a storage tank after compression.
- This embodiment demonstrates the economical course of the process according to this invention, achieving good cleaning results.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning In General (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Description
Claims (30)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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AT342/91 | 1991-02-19 | ||
AT0034291A AT395951B (en) | 1991-02-19 | 1991-02-19 | CLEANING OF WORKPIECES WITH ORGANIC RESIDUES |
PCT/EP1992/000322 WO1992014558A1 (en) | 1991-02-19 | 1992-02-14 | Process for cleaning workpieces contaminated with organic matter |
Publications (1)
Publication Number | Publication Date |
---|---|
US5980648A true US5980648A (en) | 1999-11-09 |
Family
ID=3488054
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/107,696 Expired - Fee Related US5980648A (en) | 1991-02-19 | 1992-02-14 | Cleaning of workpieces having organic residues |
Country Status (12)
Country | Link |
---|---|
US (1) | US5980648A (en) |
EP (1) | EP0571426B1 (en) |
JP (1) | JPH06505189A (en) |
AT (1) | AT395951B (en) |
AU (1) | AU1226892A (en) |
CA (1) | CA2103909A1 (en) |
CZ (1) | CZ282595B6 (en) |
DE (1) | DE59200370D1 (en) |
DK (1) | DK0571426T3 (en) |
ES (1) | ES2062889T3 (en) |
NO (1) | NO180003C (en) |
WO (1) | WO1992014558A1 (en) |
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US6306564B1 (en) | 1997-05-27 | 2001-10-23 | Tokyo Electron Limited | Removal of resist or residue from semiconductors using supercritical carbon dioxide |
US6500605B1 (en) | 1997-05-27 | 2002-12-31 | Tokyo Electron Limited | Removal of photoresist and residue from substrate using supercritical carbon dioxide process |
US20040011386A1 (en) * | 2002-07-17 | 2004-01-22 | Scp Global Technologies Inc. | Composition and method for removing photoresist and/or resist residue using supercritical fluids |
US20040050406A1 (en) * | 2002-07-17 | 2004-03-18 | Akshey Sehgal | Compositions and method for removing photoresist and/or resist residue at pressures ranging from ambient to supercritical |
US6722642B1 (en) | 2002-11-06 | 2004-04-20 | Tokyo Electron Limited | High pressure compatible vacuum chuck for semiconductor wafer including lift mechanism |
US6736149B2 (en) | 1999-11-02 | 2004-05-18 | Supercritical Systems, Inc. | Method and apparatus for supercritical processing of multiple workpieces |
US6764552B1 (en) | 2002-04-18 | 2004-07-20 | Novellus Systems, Inc. | Supercritical solutions for cleaning photoresist and post-etch residue from low-k materials |
US20040211447A1 (en) * | 2003-04-28 | 2004-10-28 | Supercritical Systems, Inc. | Apparatus and method of securing a workpiece during high-pressure processing |
US6871656B2 (en) | 1997-05-27 | 2005-03-29 | Tokyo Electron Limited | Removal of photoresist and photoresist residue from semiconductors using supercritical carbon dioxide process |
US6890853B2 (en) | 2000-04-25 | 2005-05-10 | Tokyo Electron Limited | Method of depositing metal film and metal deposition cluster tool including supercritical drying/cleaning module |
US6921456B2 (en) | 2000-07-26 | 2005-07-26 | Tokyo Electron Limited | High pressure processing chamber for semiconductor substrate |
US6924086B1 (en) | 2002-02-15 | 2005-08-02 | Tokyo Electron Limited | Developing photoresist with supercritical fluid and developer |
US6926798B2 (en) | 1999-11-02 | 2005-08-09 | Tokyo Electron Limited | Apparatus for supercritical processing of a workpiece |
US6928746B2 (en) | 2002-02-15 | 2005-08-16 | Tokyo Electron Limited | Drying resist with a solvent bath and supercritical CO2 |
US7001468B1 (en) | 2002-02-15 | 2006-02-21 | Tokyo Electron Limited | Pressure energized pressure vessel opening and closing device and method of providing therefor |
US7021635B2 (en) | 2003-02-06 | 2006-04-04 | Tokyo Electron Limited | Vacuum chuck utilizing sintered material and method of providing thereof |
US7064070B2 (en) | 1998-09-28 | 2006-06-20 | Tokyo Electron Limited | Removal of CMP and post-CMP residue from semiconductors using supercritical carbon dioxide process |
US7077917B2 (en) | 2003-02-10 | 2006-07-18 | Tokyo Electric Limited | High-pressure processing chamber for a semiconductor wafer |
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US20070017557A1 (en) * | 1999-09-24 | 2007-01-25 | Micell Technologies | Cleaning apparatus having multiple wash tanks for carbon dioxide dry cleaning and methods of using same |
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- 1992-02-14 WO PCT/EP1992/000322 patent/WO1992014558A1/en active IP Right Grant
- 1992-02-14 US US08/107,696 patent/US5980648A/en not_active Expired - Fee Related
- 1992-02-14 CZ CS931676A patent/CZ282595B6/en not_active IP Right Cessation
- 1992-02-14 DK DK92904002.0T patent/DK0571426T3/en not_active Application Discontinuation
- 1992-02-14 CA CA002103909A patent/CA2103909A1/en not_active Abandoned
- 1992-02-14 JP JP4503987A patent/JPH06505189A/en active Pending
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- 1992-02-14 EP EP92904002A patent/EP0571426B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
AU1226892A (en) | 1992-09-15 |
CZ282595B6 (en) | 1997-08-13 |
CA2103909A1 (en) | 1992-08-20 |
EP0571426A1 (en) | 1993-12-01 |
ATA34291A (en) | 1992-09-15 |
WO1992014558A1 (en) | 1992-09-03 |
AT395951B (en) | 1993-04-26 |
DK0571426T3 (en) | 1994-09-26 |
ES2062889T3 (en) | 1994-12-16 |
EP0571426B1 (en) | 1994-08-10 |
NO932938L (en) | 1993-08-18 |
JPH06505189A (en) | 1994-06-16 |
NO932938D0 (en) | 1993-08-18 |
NO180003B (en) | 1996-10-21 |
DE59200370D1 (en) | 1994-09-15 |
CZ167693A3 (en) | 1994-03-16 |
NO180003C (en) | 1997-01-29 |
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